See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/250863681

Research topics in Analytical Chemistry: some current work

in universities and college

Article  in  Proceedings of the Society for Analytical Chemistry · January 1970

DOI: 10.1039/sa9700700145

CITATION READS

1 14,675

12 authors, including:

D. Thorburn Burns William Franklin Smyth

Queen's University Belfast Ulster University
409 PUBLICATIONS   4,916 CITATIONS    175 PUBLICATIONS   4,261 CITATIONS   

SEE PROFILE SEE PROFILE

Petr Zuman
Clarkson University
580 PUBLICATIONS   6,632 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Australian stingless bees - Natural Products View project

Diffusion controled limiting currents on solid electrodes View project

All content following this page was uploaded by William Franklin Smyth on 20 January 2014.

The user has requested enhancement of the downloaded file.

 View Article Online / Journal Homepage / Table of Contents for this issue

August, 19701 RESEARCH TOPICS I N ANALYTICAL CHEMISTRY 145

Research Topics in Analytical Chemistry: Some Current Work

in Universities and Colleges
The following are summaries of some of the papers presented a t an Ordinary Meeting
of the Society held on May 7th and 8th, 1970, and reported in the May issue of Proceedings
(P. 77).
Published on 01 January 1970 on http://pubs.rsc.org | doi:10.1039/SA9700700145

Investigations into the Determination of Low Levels of Tungsten in Alloy Steels

with Heteropolyacids and Thiocyanate as Chromogenic Reagents
Downloaded by Universidad Amazonica de Pando on 09 March 2013

AND D. THORBURN
BY D. R. MARRIOTT,A. G. FOGG BURNS
(Department of Chemistry, Loughborough University of Technology, Loughborough, Leicestershire)

BECAUSE of the chemical similarity of tungsten and molybdenum, methods for the colorimetric
determination of tungsten are often unspecific in the presence of molybdenum. Chemical
separation has been achieved by the use of diaminophenylnaphthalene,l and these results
were confirmed by the present authors. A detailed study of this reaction was not made,
however, as the reagent and its precursors could possibly be carcinogenic.
A new approach in which molybdate is used as a reagent for tungsten has been tried.
It is known that tungsten will form heteropolyacids with phosphorus, germanium, selenium,
silicon, arsenic and molybdenum in acidic media. The extent of formation of heteropolyacids
is dependent on pH and temperature as well as the relative concentrations of the constituent
species. The determination can be made by direct colorimetry or by selective reduction of
the heteropolyacid to molybdenum blue, taking advantage of the accompanying amplification.
When yellow phosphomolybdic acid is added to a hydrochloric acid solution a colourless
solution is obtained, but if tungsten is present the permanent yellow colour of phospho-
molybdotungstic acid forms. This colour is stable with time, and the absorbance maximum
is at 341 nm. Although the blank is colourless it absorbs fairly strongly a t this wavelength;
the absorbance maximum of the phosphomolybdate blank is a t 299 nm, and molybdate itself,
if present, also interferes owing to a broad absorbance band that has a maximum a t 250 nm.
Selective reduction of the phosphomolybdotungstic acid to molybdenum blue was
attempted after masking excess of reagent and any molybdate present with citrate, oxalate
or tartrate. A careful balance between the concentration of the complexant and that of the
reductant [hydrazine, quinol or tin(I1) chloride] is necessary. Of the various combinations
of complexant and reductant tried, complexation with citrate and reduction with a mixture
of tin(I1) chloride and hydrazine were most promising, but even here the repeatability of the
results was unsatisfactory and molybdate interfered. The use of onium cations to stabilise
the phosphomolybdotungstic acid was investigated but again molybdenum interfered; the
usual masking agents for molybdate form complexes that are not sufficiently stable to prevent
the reduction to molydenum blue a t a similar rate to that for the reduction of phospho-
molybdot ungst ic acid.
The procedure for the determination of tungsten by extraction of the tungsten(V) -
thiocyanate anion as an onium salt has been assessed, modified and adapted for use in
determining tungsten in steels.233 Neither niobium nor vanadium interferes. The extent
of molybdenum interference depends on the iron concentration in the sample solution from
which the onium salt is extracted. At the low sample weights taken for steels containing
more than 0.25 per cent. of tungsten, molybdenum does not interfere. For low tungsten
content steels it is necessary to extract the tungsten (and molybdenum) from the iron when
the molybdenum concentration exceeds 0.3 per cent. w/w.

REFERENCES
1. Belcher, R., and Nutten, A. J., J . Chem. Soc., 1951, 1516.
2. Fogg, A. G., Marriott, D. R., and Thorburn Burns, D., Analyst, 1970, 95, in the press.
3. -,-,- , Ibid., 1970, 95, in the press.
 View Article Online
146 RESEARCH TOPICS I N ANALYTICAL CHEMISTRY CProc. SOC.AnaZyt. Chem.
A Study of Several Chromium Polyphosphate Glasses
BY F. SNAPE
(Chemistry Department, University College, Swansea, Glum.)

LITTLEattention has been paid to inorganic ion exchangers compared with organic resins.
The main reason for this is that the organic materials are produced under controlled conditions
and give reproducible products. However, their inorganic counterparts are much more
stable under certain conditions, e.g., high temperature and radiation.
Betteridge and Stradlingl prepared an inorganic ion exchanger, chromium polyphosphate
Published on 01 January 1970 on http://pubs.rsc.org | doi:10.1039/SA9700700145

glass, which had some very desirable properties. We have prepared a family of glasses with
properties closely resembling those of the original. The main purpose of this work was an
investigation into the structure, stability, ion-exchange mechanism and properties of this
Downloaded by Universidad Amazonica de Pando on 09 March 2013

family.
Typically a glass is prepared by adding an equal volume of sodium tripolyphosphate
(0.2 M) to chromic chloride (0.5 M) a t room temperature in a beaker. A tar is produced
which, if allowed to stand and dry in air, gives a glass-like product that has good mechanical
properties and may be ground to convenient mesh sizes.
Structural investigations with techniques of nuclear magnetic resonance, X-ray diffrac-
tion, mass spectrometry, differential thermal analysis, thermogravimetry, electron microscopy
and infrared spectroscopy showed that the glass was an irregular amorphous polymer.
Stability investigations involved the determination of the dissolution time and the
form of the dissolution curve (for which an empirical equation has been used) with different
solvents. It was found that the family was amply stable for most practical ion-exchange
processes.
The ion-exchange properties involved batch, kinetic and column studies. Batch uptake
of alkali and polyvalent metal ions showed that the alkali metal ions are the strongly preferred
ions. Titration curves have been obtained by Topp and Pepper’s method2 and these showed
various inflection points. Correlations have been obtained between the uptake of the alkali
metal ions and other properties such as the infrared spectra and the phosphorus-to-chromium
mole ratio.
Kinetic studies with Boyd and Soldano’s method3 have been carried out and it was
found that particle diffusion control operated a t the higher concentration levels.
Separation of sodium and caesium on a column of the glass was easily accomplished by
using 1 M hydrochloric acid and 1 M lithium sulphate as eluents a t different elution rates.
A family of glasses has been prepared cheaply, easily and quickly; it has good mechanical
properties and seems to be a good compromise inorganic ion exchanger.
REFERENCES
1. Betteridge, D., and Stradling, G. N., J . Inorg. Nucl. Chern., 1967, 29, 2652.
2. Topp, N. E., and Pepper, I(.W., J . Chem. SOC.,1949, 3299.
3. Boyd, G. E., and Soldano, B. A., J , Arner. Cheun. SOG.,1954, 75, 6091.

Metallochromic Indicator Coniplexes as ,Acid Base Indicators -

BY ROBERTA. CHALMERSAND FRANK
I. MILLER
(Depnrtment of Chemistry, University of ,4 bevdeen, Old ,4 berdeen, S c o t l a d )

WHENthe formation of metal - metallochromic indicator complexes is accompanied by the

release of more than one proton per indicator molecule complexed, the colour change a t the
end-point is sharper than that of a conventional acid - base indicator, where only one proton
is released. The greater the number of protons released per indicator molecule, the sharper
the colour change. Because complexes of different stability are formed between metals and
metallochromic indicators, one such indicator can provide a whole range of pH indicators
by variation of the metal ion used. The pK value for the indicator system is a conditional
constant, and can be lowered by increasing the amount of free metal ion present or by in-
creasing the concentration of the indicator complex. The nature of the metal - indicator
 View Article Online
August, 19701 RESEARCH TOPICS I N ANALYTICAL CHEMISTRY 147
complex can be deduced from a study of the absorbance - pH curve for different ratios of
metal ion and indicator concentrations. Either component of the indicator system can be
determined by potentiometric (pH) titration with the other. Limitations are imposed by
the necessity to avoid the presence of species forming more stable complexes with the metal
ion, by hydrolysis, and by the acid - base characteristics of the free indicator. In the most
favourable cases it is possible to achieve a complete colour change over 0.5 pH unit or less.

Polarographic Study of Substituted 2-Thiobarbituric Acids

Published on 01 January 1970 on http://pubs.rsc.org | doi:10.1039/SA9700700145

BY W. F. SMYTH,
G. SVEHLA
AND P. ZUMAN*
(Department of Chemistry, T h e Queen’s Uwiversity of Belfast, Northem Ireland)
Downloaded by Universidad Amazonica de Pando on 09 March 2013

THE barbiturate and thiobarbiturate series, since the discovery of the hypnotic properties
of 5,5’-diethylbarbituric acid a t the beginning of the century,l ,2 have been considerably
y3

developed, to the extent that they have become invaluable sedatives, hypnotics, anaesthetics
and anticonvulsants. Although they are usually assayed by volumetric and spectrophoto-
metric methods, polarographic methods of analysis possess certain advantages over these
traditional methods .
The thiobarbiturates show4anodic polarographic phenomena corresponding to the forma-
tion of slightly soluble mercury compounds, similar to other sulphur-containing compound^.^
Adsorption phenomena involved depend on the structure of the thiobarbiturate to such a
degree that it is possible to distinguish between various derivatives on this basis, e.g., in
1 M sodium hydroxide, thiobarbiturates give two waves the sum of which is a linear function
of the concentration, but this does not hold for the more negative wave. If the 5,5’-disubsti-
tuted derivatives with straight and branched-chain alkyl groups are compared, the more
negative wave is, in all cases, larger for the compounds with straight chains than for the
derivatives with branched chains.
Most 2-thiobarbituric acids, however, can be reduced under polarographic conditions,
and display a wide variety of cathodic phenomena over the pH range from 2 to 12. The
5,5’-disubstituted species, I, are reduced in a four-electron process for 3 < p H < 4, and in
a two-electron process for 5 < p H < 12, whereas those substituted in the 1, 5- and 5‘-posi-
tions, 11, are reduced in a two-electron step (6 < p H < 12). The 1,3,5,5’-tetrasubstituted
species, 111, are reduced over p H range 2 to 12.

R, C0.N
7
’c\ ‘cs
/\ /
R, C0.N
\
R4
I . . . Rl= R, = alkyl or olefinic; R, = R, = H
I1 . . . R, = R, = alkyl or olefinic; R, = alkyl; R, =H
I11 . . . R, = R, = R, = R, = alkyl.
The reduction waves, which cannot be used for differentiation of classes of thiobarbi-
turates as they give waves a t similar half-wave potentials and of comparable height, offer
a wider concentration range for analysis than anodic waves, and their heights can usually
be measured with a higher degree of accuracy. When 2-thiobarbiturates are present in the
sample with other electroactive substances, the choice of using either cathodic waves (usually
in 0.05 M borax supporting electrolyte) or anodic waves (in 0.1 M or 1 M sodium hydroxide)
should be made according to the properties of the other electroactive species, in particular
whether they give more positive reduction waves or more negative anodic waves than thio-
barbiturates. The cathodic wave is nevertheless a $ h r i recommended for the determination
of 1,5,5‘-trisubstituted thiobarbiturates, 11, which in alkaline media, pH > 11, undergo rapid
hydrolysis.
* Present address: Department of Chemistry, Clarkson College of Technology, Potsdam, N.Y., U.S.A.
 View Article Online
148 RESEARCH TOPICS IN ANALYTICAL CHEMISTRY [Proc. SOC.Amalyt. Chew.
REFERENCES
1. Fischer, E., and von Mering, J., Therapie Gegenw., 1903, 44, 97.
2. -,- , Ibid., 1904, 45, 145.
3. Hoesch, K., “Emil Fischer: Sein Leben und Sein Werk,” Berichte Sonderheft, 1921, 54, 241.
4. Zuman, P., Colln Czech. Chem. Commun., 1955, 20, 649, 876 and 883.
5. Brezina, M., and Zuman, P., “Polarography in Medicine Biochemistry and Pharmacy,” Inter-
science Publishers, New York, 1958.

The Atomic-spectroscopic Determination of Ruthenium

Published on 01 January 1970 on http://pubs.rsc.org | doi:10.1039/SA9700700145

BY W. B. ROWSTON,
J. M. OTTAWAY
AND MRS. M. STULIK
(Department of Pure and Applied Chemistry, University of Strathclyde,
Downloaded by Universidad Amazonica de Pando on 09 March 2013

Cathedral Street, Glasgow, C.l)

ANALYTICAL methods involving such techniques as neutron-activation analysis, spectrophoto-

metry and catalysis are commonly used for the determination of ruthenium in aqueous solution.
These techniques, however, lack specificity and often require prior separation of ruthenium
from several possible interferences including the co-presence of other noble metals. Atomic-
absorption, flame-emission and spectrographic analyses have been successfully applied to the
determination of almost all metals, but little information has been reported1 on the application
of these techniques to the determination of noble metals, especially ruthenium and osmium.
The paper reported the results of investigations of the many interferences encountered in
the atomic-emission and absorption determination of ruthenium, and described the develop-
ment of a satisfactory procedure for the atomic-spectroscopic determination of ruthenium in
aqueous solution, which does not require the prior separation of ruthenium from other species.
The emission spectrum from a ruthenium hollow-cathode lamp is complex and for good
sensitivity in atomic-absorption spectrophotometry a monochromator of high resolving power
is necessary to isolate the more sensitive ruthenium resonance lines from other neighbouring
non-absorbing lines. In the wavelength range of interest, this requirement is best satisfied
by using an instrument with a grating monochromator with reasonable resolving power,
such as the Perkin-Elmer 290 used in the present work. The emission spectrum of ruthenium
from solution, however, is comparatively simple and consists mainly of ruthenium resonance
lines conveniently situated in a spectral region between the OH band a t about 330 nm and
the first band of C, a t about 380 nm. In this region the background radiation from an air -
acetylene flame is sufficiently low to permit the determination of ruthenium by flame- (and
electrical) emission spectrophotometry.
The chemical effects of a wide variety of inorganic and organic compounds were investi-
gated for their interference on the atomic-absorption and atomic-emission signals of ruthenium.
The effect of varying the concentration of each interference was also investigated. Similar
effects were observed in the three techniques. In general, the interference effects depressed
the ruthenium signal but some compounds, notably copper and most noble metal chlorides,
caused an enhancement. Organic and mineral acids, including both oxyacids and, for
example, hydrobromic and hydriodic acids, caused suppression of the ruthenium signal ; this
is probably caused by the formation of thermally stable compounds in the flame. This is
supported by the fact that the effects are less pronounced in flames of high temperature,
e.g., the nitrous oxide - acetylene flame. In contrast to the effects of free mineral acids, it
was observed that oxyanion salts of metals, in general, caused an increase in the spectroscopic
signal for ruthenium, whereas metal halides generally caused a suppression. For example,
similar behaviour was observed for salts of sodium, magnesium, aluminium, iron and cadmium.
Almost every compound investigated produced an interference effect.
Normal methods of removing the numerous interferences found in the determination of
ruthenium were unsuccessful as the commonly used releasing agents, such as 8-hydroxy-
quinoline and EDTA, themselves cause serious depressive interference. Recently, Schnepfe
and Grimaldi? following the work of Strasheim and W e ~ s e l shave
, ~ shown that similar inter-
ference phenomena in the atomic-absorption determination of palladium and platinum can be
controlled bythe addition of a mixture of copper and cadmium ions to both standard and
sample solutions. We have applied this procedure with equal success to the determination of
 View Article Online
August, 19701 RESEARCH TOPICS I N ANALYTICAL CHEMISTRY 149
ruthenium by all three techniques discussed above. A plot of atomic-absorption signal for
25 p.p.m. of ruthenium verszts increasing concentration of copper and cadmium sulphates was
observed to attain a maximum absorption a t 0.5 per cent. each of copper and cadmium. An
addition of this optimum concentration was therefore made to all standard and sample
solutions. A calibration plot of atomic-absorption signal veYsus ruthenium concentration in
the presence of the optimum copper - cadmium concentration gave a linear graph over the
range of 0 to 60p.p.m. of ruthenium by using the most sensitive resonance wavelength,
349.9 nm. The addition technique was found to eliminate the interference effects of all
compounds investigated a t concentrations below 300 p.p.m. of interferant. For most com-
pounds, protection from interference was effective up to 2000 p.p.m. This procedure thus
Published on 01 January 1970 on http://pubs.rsc.org | doi:10.1039/SA9700700145

provides a satisfactory method for the determination of ruthenium a t this concentration

level in almost any matrix and the determination of ruthenium in a number of ruthenium
complexes was described.
Downloaded by Universidad Amazonica de Pando on 09 March 2013

In view of the simplicity of operation, specificity, low cost and high sensitivity (0.5 p.p.m.
of ruthenium in a slightly fuel-lean air - acetylene flame) the atomic-absorption spectrophoto-
metric technique is recommended for the determination of ruthenium in aqueous solution
without prior separation from other species. The flame-emission and spectrographic techniques
were found to be only slightly less sensitive than the atomic-absorption process but are
subject to much spectral interference especially from transition metals such as iron and nickel.
The ruthenium line best suited to emission work is 3724 nm.
REFERENCES
1. Beamish, F. E., Lewis, C. L., and Van Loon, J. C., Talanta, 1969, 16, 1.
2. Schnepfe, M. M., and Grimaldi, F. S., Ibid., 1969, 16,591.
3. Strasheim, A, and Wessels, G. J., A p p l . Spectrosc., 1963, 17, 65.

The Spectrophosphorimetric Determination of Zinc with 2( 2 -Hydroxyphenyl)-

benzoxazole
Bu P. R. WOODAND L. S. BARK
(Chemistry Department, University of Salford, Salford 5, Lancs.)
THEprocesses involved in photoluminescence and the advantages of phosphorimetry over
fluorimetry for the determination of trace quantities of metal ions were described.
The need to use rigid media for the observation of phosphorescence prompted the
examination of a variety of solvents with regard to their ability to form optical glasses
at the temperature of liquid nitrogen. Ethanol was shown to be the most suitable solvent
for work with inorganic ions because 10 to 12 per cent. v/v of water could be added without
resulting in cracked glasses, which cause scattering of the incident radiation.
With non-aqueous solvents it is impossible to measure pH values with conventional
equipment. However, control of the acidity of solutions was achieved by adding small
amounts of aqueous ammonium acetate, acid - ammonia solution buffers, and reproducible
conditions were obtained.
An investigation of the phosphorescence characteristics of 2(2’-hydroxyphenyl) benzoxa-
zole and its metal chelates showed that the zinc chelate was highly phosphorescent and exhibited
a considerable shift in wavelengths of maximum excitation and emission compared with
those of the reagent. The parameters necessary to establish a method for the determination
of zinc with 2(2 -hydroxyphenyl)benzoxazole were systematically investigated.
The effect of acidity on the phosphorescence intensity of the reagent and the zinc chelate
was investigated. The optimum “nominal pH” (the pH of the aqueous buffers) was 6.4.
The variation in the phosphorescence of the zinc chelate with change in pH showed that two
different chelates were possibly formed a t nominal pH of 6.4 and 7-4.
Subsequent work was carried out with a minimum of 100-fold molar excess of the ligand.
A calibration graph was produced with a fixed amount of the reagent, suficient a t the
maximum zinc concentration to ensure that 100-fold molar excess of ligand was present.
The calibration graph (Beer’s law plot) was linear in the solution a t a final concentration of
zinc of between 2-5 and 40ngml-l. Thus the amount of zinc that could be determined
in an aqueous solution was 45 t o 1000 ng ml-1.
 150 RESEARCH TOPICS IN ANALYTICAL CHEMISTRY [Proc. Soc.View Article Online
A.tzaZyt. Chew.
The proposed method for the determination of zinc is comparable in sensitivity with
previously published methods, and shows fewer interferences. The metal ions Be2+, Au3+,
Ni2+ and Fe3+ interfere by increasing the intensity, while Cu+, Hg+ and Pd2+interfere by
reducing the intensity. Sulphide and EDTA2- also interfere by reducing the intensity.
The nature of the chelates formed was studied by the method of continuous variation
(Job’s plot) a t nominal p H 6.4 and 7.4. At both values a 1 : 1 metal - ligand complex was
formed. The solid complex isolated from concentrated solutions was of the form ML,.
It was suggested that the two complexes in dilute solutions are a t a nominal pH 6.4,
[Zn(EtOH),L]+OAc-; and a t a nominal pH 7.4, [Zn(EtO)(EtOH)L].
Published on 01 January 1970 on http://pubs.rsc.org | doi:10.1039/SA9700700145

The Hyctyolysis of Cyanogen Chloride

Downloaded by Universidad Amazonica de Pando on 09 March 2013

BY P. L. BAILEYAND E. BISHOP
(Chemistvy Depavtment, The Univevsity, Stocker R o a d , Exetev, Devon)
THEhydrolysis of cyanogen chloride is the rate determining and most important step in
the chlorination process for the destruction of cyanide in industrial effluents, and some studies
of the processes involved have been made.ls2y3 Some of the earlier work has been repeated
to establish a basis for catalytic investigations, to extend the range of conditions examined
and to penetrate more deeply into the reaction mechanisms and their controlling parameters.
The hydrolysis is usually formulated as
CNCl +
OH- -+ C1- HOCN +
and the cyanic acid will ionise in accord with the pH of the solution. The order with respect
to hydroxyl ion was first examined by carrying out a series of hydrolyses a t constant tem-
perature over a range of fixed hydroxyl concentrations maintained by borax buffers, the
pH being continuously monitored to confirm constancy. A closed system is necessary to
prevent loss of cyanogen chloride by volatilisation. The reaction was followed by withdrawing
samples at intervals and determining the cyanogen chloride concentration spectrophoto-
metrically by a simplification of the method of Bark and Higson.* Initial concentrations

3 4 5 6

PO H

Fig. 1. Hydroxyl dependence

of cyanogen chloride were of the order of 1 0 - 4 ~or 6 p.p.m. Excellent rectilinear plots of
the logarithm of the cyanogen chloride concentration against time were obtained, showing
that the reaction is precisely first order with respect to cyanogen chloride, and first-order
rate constants were calculated from the slope of these plots for each pH value. In Fig. 1,
the relationship between these pseudo first-order rate constants, k‘, and p H over the range
7.3 to 11-2 is shown as a plot of -log,, k’ against pOH (= pK, - pH). At higher hydroxyl
 View Article Online
August, 19701 RESEARCH TOPICS I N ANALYTICAL CHEMISTRY 151
concentrations thc order closely approaches unity, 0.96 at pOH = 3 to 4,but a t lower hydroxyl
concentrations the order drops, to 0.80 a t pOH = 6. Although two straight lines are shown in
Fig. 1, the transition is smooth. This suggests that there are two simultaneous processes:
direct reaction with hydroxyl ion which preponderates a t high pH values, and reaction with
water which increases in importance as the pH falls. From hydrolyses a t diverse temperatures
from 5" C (half-life 10 hours) to 45"C (half-life 1 minute), an Arrhenius activation energy
of 14.1 kcal mol-l has been calculated. The system does not show specific buffer effects.
The effects of numerous additives have been examined with a view both to assist
mechanistic interpretation and to discover possible accelerators or catalysts. Metal ions
such as iron(I1) and mercury(I1) are without effect, but nickel(I1) a t a concentration of
Published on 01 January 1970 on http://pubs.rsc.org | doi:10.1039/SA9700700145

10 p.p.m. increased the rate by about 10 per cent. Phosphate, which has been reported to
catalyse the hydrolysis,l has no effect, nor have chloride, perchlorate, carbonate or bicarbonate.
Downloaded by Universidad Amazonica de Pando on 09 March 2013

0 10

Time, minutes
Fig. 2. Effect of additives: A, control; B, NH,+; C, CN-; D, Cl,; and B,
so,
The accelerating effect of some other species on the rate of destruction of cyanogen
chloride a t pH= 10.1 is shown in Fig. 2. Initial concentrations of both additive and cyanogen
chloride were lo-* M ; the control plot shows the rate of hydrolysis in the absence of any
additives; the ordinate is - l o g , ~ t / A , where A t is the absorbance a t time t, and A , is the
absorbance a t time zero, and is proportional to -log,,[CNCl]. Ammonia (added as ammonium
ion) shows the smallest effect; this is not due to accelerated hydrolysis but to enhancement
of the rate of removal of cyanogen chloride by a subsidiary chemical reaction to form
cyanamide. A possible explanation for the effect of cyanide could be the formation of a
1: 1 adduct of cyanide and cyanogen chloride, as reported by Pungor5; it is not unlikely
that an adduct of this nature would hydrolyse more rapidly than cyanogen chloride.
Sulphur dioxide bleached the dyestuff formed in the determination of cyanogen chloride,
but this interference could be quantitatively eliminated by precipitation and centrifugation
of barium sulphite. Cyanogen chloride disappears rapidly in the presence of sulphur dioxide,
the half-life a t pH = 10.1 being 4 minutes. Determination of sulphur dioxide before and after
the reaction showed that sulphur dioxide is consumed in 1: 1stoicheiometry with the cyanogen
chloride. If the sulphur dioxide acts as a reducing agent, then the obvious product would
be cyanide, but tests by three independent methods for cyanide were negative, showing that
1 per cent. a t the most, and probably none, of the cyanogen chloride was converted into
cyanide. This reaction is under investigation.
 View Article Online
152 MEMBERSHIP CHANGES [Proc. SOC.APzalyt. Chew.
Chlorine interfered in the determination by oxidising the 1,4-diaminobenzene used in
the Bark and Higson method: this interference was eliminated by treatment with bromide
and arsenic(II1) after acidification and before development of the colour. Catalysis by chlorine
species poses substantial problems. In early experiments, the chlorine was added in the
form of an aliquot of sodium hypochlorite solution, prepared by passing excess of chlorine
into sodium hydroxide solutions : drastically varying hydrolysis rates were obtained. With
freshly prepared hypochlorite the cyanogen chloride was destroyed extremely rapidly, but,
as the hypochlorite solution aged, its catalytic power decreased until, after the lapse of
2 weeks, addition of an aliquot containing the same available chlorine content as the original
fresh solution produced no acceleration of hydrolysis a t all. The example shown in Fig. 2
Published on 01 January 1970 on http://pubs.rsc.org | doi:10.1039/SA9700700145

is one of the faster hydrolyses a t this pH, the half-life being about 5 minutes compared
with 17 minutes for the control. At pH = 9-2 and with a fairly fresh hypochlorite solution a
half-life of 1.5 minutes, compared with 90 minutes for the control, was obtained. In none of
Downloaded by Universidad Amazonica de Pando on 09 March 2013

these reactions did analysis before and after indicate any consumption of chlorine It was
clearly necessary to discover which of the species present in such a hypochlorite solution was
responsible for the catalysis. Additions of perchlorate, chlorate, chloride and chlorine dioxide
produced no catalysis. Chlorite gave a rate constant 15 per cent. higher than the control, but
this is a relatively trifling effect and, furthermore, the amount of chlorite in the hypochlorite
solution will be small. This left three species: molecular chlorine, hypochlorous acid and
hypochlorite ion: but a t pH= 10 little chlorine or unionised hypochlorous acid could be expected
to remain, although all three will be in equilibrium in the presence of chloride. Chlorine
(and chloride which has no catalytic effect) was removed from the stock hypochlorite by addi-
tion of mercury(I1) oxide, and the resultant solution produced no catalysis in the p H range
9 to 10, but addition of fresh chlorine water to the reaction mixture again produced a great
acceleration of hydrolysis. It is reasonable to conclude that molecular chlorine is the active
catalyst, yet it is difficult to accept that any considerable amount of free chlorine remains
unhydrolysed a t pH=9 to 10. However, the catalysis becomes more marked as the pH de-
creases, which supports the conclusion ; so does the loss of catalytic activity as the hypochlorite
ages with gradual removal of excess of chlorine from the solution. If the p H is lowered too
far, chlorine will react directly with the cyanate produced in the hydrolysis, and this will
consume chlorine and mask its effect on the hydrolysis. The mechanism is still under
examination.
REFERENCES
1. Price, C . C., Larson, T. E., Beck, K. M., Harrington, F. C., Smith, L. C., and Stephanoff, I., J .
Anzer. Chew. SOC.,1947, 69, 1640.
2. Eden, G. E., and Wheatland, A. B., .J. SOC.Chem. Ind., 1950, 69, 166.
3. Eden, G. E., Harnpson, B. L., and Wheatland, A. B., Ibid., 1950, 69, 244.
4. Bark, L. S., and Higson, H. G., Talanta, 1964, 11, 471 and 621.
5. Pungor, E., and Schulek, E., A n n . Univ. Scient. Budapest Roland0 Eotvos Nomiuzatae, Sec. Chim.,
1960, 2,99.

View publication stats